JP6478165B2 - Powdered diacetal clearing agent and method for producing the same - Google Patents

Description

  The present invention relates to a powdery diacetal clearing agent used for plastics such as polyolefin, and more specifically to a powdery diacetal clearing agent containing di (arylidene) -D-sorbitol. The present invention also relates to a method for producing a powdery diacetal clearing agent.

  Transparent plastic parts made of polyolefin are those whose contents can be made visible and have therefore been used in a wide variety of industries. The action of di (arylidene) -D-sorbitol as a polyolefin nucleating agent is useful for reducing molding time and improving the physical properties of polyolefin products. Di (arylidene) -D-sorbitol can also be used as a clearing agent to increase the transparency of semi-crystalline polyolefin products.

What is generally recognized in the mechanism of di (arylidene) -D-sorbitol is the following point.
For example, a diacetal powder, such as di (arylidene) -D-sorbitol powder, is added to the polyolefin and then melted at an appropriate temperature before it is crystallized and dispersed during the cooling and molding process of the polyolefin plastic. The crystal network is developed by the crystallized and dispersed diacetal powder. In the crystal network, a plurality of spherical nucleation sites are formed. The plurality of nucleation sites are so small that they do not scatter visible light, thereby making the polyolefin article transparent. Accordingly, transparent plastic products are widely used in household items, large-scale containers, electronic devices, medical devices, automotive anti-freezing products, and food packaging products.

  Di (arylidene) -D-sorbitol derivatives such as 1,3: 2,4-di (4-methylbenzylidene) -D-sorbitol (MDBS), 1,3: 2,4-di (4-chlorobenzylidene) -D-sorbitol (CDBS), 1,3: 2,4-di (4-ethylbenzylidene) -D-sorbitol (EDBS), 1,3: 2,4-di (3,4-dimethylbenzylidene) -D -Sorbitol (DMDBS), di (methyl-tenylidene) -D-sorbitol (MDTS), etc. are generally disclosed in patent publications or used for the development of commercially available compounds.

Taiwan Patent Application Publication No. 201439095 US Patent Application Publication No. 2009/0111918 US Patent Application Publication No. 2007/0060697 U.S. Pat.No. 4,429,140 U.S. Pat. No. 5,023,354 US Pat. No. 5,731,474 Taiwan Patent Application Publication No. 200407376 Taiwan Patent No. I318994 European Patent Office Invention Specification No. 1505109 Taiwan Patent Application Publication No. 2015540762 Chinese Patent Application No. 103391966 Taiwan Patent No. I270529 Taiwan Patent No. I353998

  However, since conventional plastic products are repeatedly concerned about safety, transparency, appearance, and quality, the development of plastic products that meet the marketing requirements has become an important issue in related fields. . Conventional powdery diacetal clearing agents have the following problems to be solved.

  First, there is a long-awaited desire to solve problems such as poor dispersion due to the reduction in diameter of conventional powdered diacetal clearing agent particles and aggregation due to the heavy storage load.

  When the particle size of a conventional powdered diacetal clearing agent added to a polyolefin is too large to be adequately dispersed in the polyolefin, the product made of the polyolefin will always show visible white spots and will be identified as defective. Will be. In addition, in order to reduce the size of the conventional powdery diacetal transparent agent, it is necessary to spend extra energy for the polishing treatment, so that the product yield is reduced and the manufacturing cost is increased.

  Even if the poor dispersion and aggregation can be overcome, the conventional powdery diacetal clearing agent having a small diameter tends to aggregate, has a large friction, and water adheres at a large surface area. As a result, the fluidity is lowered by the inner wall of the device, and other problems such as undesirable adhesion occur in the process related to the conventional powdery diacetal clearing agent.

  A more serious problem is that the static electricity generated during the pulverization process not only makes the conventional powdered diacetal clearing agent more likely to scatter but also more agglomerates. As a result, visible white spots appear on the polyolefin product and are identified as defective as before.

For example, Patent Document 1 (Sukuhiro et al., Shin Nippon Chemical Co., Ltd.) includes component (A): specific diacetal, component (B): polyoxyethylene sorbitan C8-C22 fatty acid ester, and component (C): specific A composition comprising a powdered diacetal containing a fatty acid metal salt is disclosed.
Patent Document 1 uses an antistatic agent and a slip agent, and tries to avoid the diacetal powder that is stored in a tube, a supply box, or a feeder from being hardened and unnecessary adhesion and crosslinking in the diacetal powder. Unfortunately, the remaining slip agents and antistatic agents have a problem of lowering the safety of food packaging because they cannot be used directly in various fields due to heat resistance at high temperatures.

  Patent Document 2 (Tsou et al., Quotin Chemical Co., Ltd.) discloses a method for preparing a diacetal clearing agent. Crude oil production resulting from reaction with polyols in the presence of aromatic aldehydes, acid catalysts, added silanized fumed silica having a pH value of 5.5 to 8, controlled particle size, ultra fine powder diacetal composition Can be prepared. Therefore, the highly dispersed powdery diacetal composition does not generate white spots that appear to be plastic products. However, certain equipment must be used to prevent the diacetal powder from floating in the air during the process.

  Second, in order to improve the convenience of operation, it was necessary to improve the fluidity of the conventional diacetal clearing agent powder.

  To increase fluidity, conventional methods in the prior art mix fluidizers such as fumed silica (surface pH value less than 4), calcium stearate with a small amount of fatty acid remaining, and slip agent. When the diacetal clearing agent powder is employed at a high temperature, the remaining trace amount of acid causes deterioration and yellowing of the plastic, so that the appearance is finally deteriorated.

  For example, Patent Document 3 (Li et al.) Discloses blending a commercial diacetal powder clearing agent with fume silica for improving fluidity. However, in order to prevent the composition having diacetal powder from floating in the air, the use of specific equipment was inevitable.

  Third, a problem that must be improved in conventional diacetal clearing agent powders is to suppress yellowing, odor emission, and color shift of the final product during the process of processing the plastic.

  Patent Document 4 (Murai et al.) Discloses a method for producing a dibenzylidene sorbitol (DBS) clearing agent. In this method, sorbitol is reacted with benzaldehyde or an alkyl acetal derivative with an acid catalyst, a hydrophobic organic solvent, and a water-soluble organic polar solvent, but it is said that malodor occurs in the conventional process. There were drawbacks.

U.S. Patent No. 6,057,028 (Murai et al.) Disclosed another method for producing diacetal. Neutralizing, filtering, and washing a condensation product obtained by subjecting a benzoic aldehyde, a polyol having five or more hydroxyl groups, and an aryl sulfonic acid to a condensation reaction in an aqueous solution. Gives 1,3: 2,4-di (substituted benzylidene) sorbitol having a purity of 95% or more.
Other acetal production methods described in US Pat. No. 6,057,049 (Scrivens et al., Milliken Research Corporation) include benzaldehyde, polyols having five or more hydroxyl groups, acid catalysts, hydrophobic organic solutions, divalent An additive selected from the group consisting of alcohol, trihydric alcohol and tetrahydric alcohol is subjected to a heat condensation reaction and then purified to obtain 1,3: 2,4-di (substituted benzylidene) sorbitol. It is done.
The acetal obtained by Patent Document 6 has a purity of up to 97%, but none of Patent Document 4, Patent Document 5 and Patent Document 6 can prevent malodor and yellowing that occur in a high temperature environment.

In Patent Document 7, Patent Document 8, and Patent Document 9 (Masahide et al., Shin Nippon Chemical Co., Ltd.), a diacetal composition containing a diacetal and a long-chain aliphatic alcohol or a carboxylic acid having a hydroxyl group dissolves the diacetal. The nucleating agent is used as a nucleating agent that lowers the temperature to suppress the dissipation of alcohol or suppresses the movement of odor components. Furthermore, the said patent document discloses the inhibitor which suppresses odor containing a diacetal, the saturated or unsaturated fatty alcohol of C6-C32, and an anionic surfactant or at least 1 sort (s) of aliphatic amine.
However, in many cases, high temperatures are required to obtain the desired transparency and molding, and insufficient heat resistance often shifts the color of plastic products. In addition, the disclosed highly lipophilic inhibitors have been feared to be transferred by greasy foods.

  Patent Document 10 (Tsou et al., Quotin Chemical Co., Ltd.) discloses a method for producing a diacetal clearing agent. This method increases the purity of the diacetal clearing agent by removing odor releasing impurities with a hydrogenating agent.

  However, the above disclosure describes a method for preventing diacetal from being partially decomposed by residual acid in a diacetal clearing agent used with an antioxidant, a flow agent, a filler, a pigment, or a slip agent. Does not mention anything. Thus, the problem of yellowing and lack of transparency still exists in the prior art.

In the process of processing plastic products, it is common to incorporate optical brighteners or pigments into the plastic composition. Patent Document 11 discloses that a pigment is added to a conventional powdery sorbitol diacetal clearing agent in order to change visual recognition.
However, the impact on visual perception depends on the mixing ratio and mixing uniformity. In addition, the safety of fluorescent brighteners and pigments also limits the range of use of plastic products.

  Thus, there is a need to overcome or improve the negative effects of conventional diacetal clearing agents, and how to improve the overall performance of transparent plastic products while maintaining the safety of diacetal clearing agents It is an important issue.

An object of the present invention is to improve a powdered diacetal clearing agent and provide the following technical effects in a plastic product manufactured using the powdered diacetal clearing agent.
1. Low yellowness index, simple operation, and good heat resistance.
2. Prevention of odor generation during plastic processing.
3. Good tolerance to withstand high temperatures when mixing plastic raw materials.
4). Good color stability in final plastic products made with powdered diacetal clearing agents.
5. Improved visual properties of finished plastic products made with a transparent appearance and powdered diacetal clearing agent.

  In order to achieve the above-mentioned objects and technical effects, the present invention provides a suitable powdery diacetal clearing agent for use in polyolefins. The powdery diacetal clearing agent comprises (A) a specific diacetal compound and (B) an inorganic silicon compound having a pH value of 6 to 12.

  The powdery diacetal clearing agent according to the present invention provides good fluidity and good dispersibility in order to prevent scattering or solidification after storage, and thus the carrying operation is facilitated. The powdery diacetal clearing agent also has good dispersion to avoid agglomeration when the polyolefin material is added. Therefore, the powdered diacetal clearing agent improves the transparency and nucleation uniformity of the polyolefin product. In particular, it provides good resistance to high temperatures during the process, does not emit odors and has good color stability during the process.

  Preferably, the powdery diacetal clearing agent according to the present invention has a specific diacetal compound and an inorganic silicon-containing compound uniformly dispersed in the diacetal compound. Preferably, the powdered diacetal clearing agent has 96.5% by weight or more of a diacetal compound and 0.02% by weight to 3.5% by weight of an inorganic silicon-containing compound. Preferably, the powdered diacetal clearing agent has 98.5% by weight or more of a diacetal compound and 0.02% by weight to 1.5% by weight of an inorganic silicon-containing compound. Preferably, the powdered diacetal clearing agent has 99% by weight or more of a diacetal compound and 0.02% by weight to 1% by weight of an inorganic silicon-containing compound.

The diacetal compound according to the present invention is selected from the group consisting of compounds represented by general formulas (I) to (V).

Here, R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, 1 to 4 carbon atoms, fluoro, It may be an alkoxycarbonyl group having chloro and bromo. a and b are each independently an integer selected from 0 to 3;

  For example, the diacetal compound is 1,3: 2,4-di (5-methyl-2-tenylidene) -D-sorbitol. 1,3: 2,4-di (4-methylbenzylidene) -D-sorbitol. 1,3: 2,4-di (4-n-butylbenzylidene) -D-sorbitol and 1,3: 2,4-di (3,4-dimethylbenzylidene) -D-sorbitol may be used. However, it is not limited to these.

  The inorganic silicon-containing compound according to the present invention is an inorganic silicon-containing fine powder that can be dispersed in an organic polar solvent or an aqueous suspension. The inorganic silicon-containing compound has a median particle size of less than 15 micrometers and a pH value of 6-12.

  Preferably, the inorganic silicon-containing compound has a pH value of 8 or more and 10 or less, and a median particle size of the inorganic silicon-containing compound is 10 micrometers or less.

For example, in the first embodiment, the inorganic silicon-containing compound is a exfoliated montmorillonite silica nanomaterial having a median particle size of less than 1 micrometer, and the exfoliated montmorillonite silica nanomaterial has a pH value of 9 to 10. It is.
In a second embodiment, the inorganic silicon-containing compound is lithium magnesium oxide sodium silicate having a median particle size of less than 50 nanometers, and the pH value of the lithium magnesium oxide sodium silicate is 9-10.
In a third embodiment, the inorganic silicon-containing compound is sodium aluminosilicate containing a trisulfur radical anion (S3).

  Preferably, the amount of the inorganic silicon-containing compound is 0.02 wt% to 3.0 wt% based on the total amount of powdered diacetal clearing agent. Preferably, the amount of the inorganic silicon-containing compound is 0.02% by weight to 1.0% by weight based on the total amount of the powdered diacetal clearing agent.

  The present invention also provides a method for producing a powdery diacetal clearing agent comprising the following steps. (1) A step of reacting sorbitol and an aromatic aldehyde in an alcohol solvent in the presence of an organic acid catalyst to obtain a diacetal mixture. (2) adding an inorganic hydrogenating agent to remove impurities in the diacetal mixture; (3) A step of adding an inorganic silicon-containing substance having a pH value of 6 to 12. (4) filtering the mixture to remove impurities and drying the mixture to obtain a powdered diacetal clearing agent.

  The powdered diacetal clearing agent modified with an inorganic silicon-containing material has good flowability and can overcome the problem of powder scattering into the air and the problem of agglomeration. More specifically, the powdery diacetal clearing agent is excellent in thermal stability, appearance, and color stability as compared with conventional diacetal products.

  In addition, when mixing at 220 to 230 degrees Celsius, or when injected with a die, the powdered diacetal clearing agent according to the present invention does not emit an unbearable malodor. Visible white spots are not displayed on the plastic plaque produced using the powdered diacetal clearing agent according to the present invention. More preferably, the powdered diacetal clearing agent has better color stability than commercially available products. In particular, it is useful for improving the appearance and visual aesthetics of plastic molded articles.

The method of preparing a powdered diacetal clearing agent according to the present invention includes the following steps:
(A) A step of obtaining a first reaction mixture by mixing an aromatic aldehyde, a polyol, and an acid catalyst in an organic polar solvent. The equivalent ratio of the aromatic aldehyde to the polyol is 2: 1 to 2: 2.
(B) obtaining a second reaction mixture by adding a hydrogenating agent and an inorganic silicon-containing agent to the first reaction mixture; The equivalent ratio of the hydrogenating agent to the aromatic aldehyde is greater than 0.01: 1, the inorganic silicon-containing agent has a pH value of 6 to 12, and the amount of inorganic silicon-containing agent used is aromatic. From 0.02% to 3.5% by weight, based on the amount of aldehyde.
(C) A step of obtaining a powdery diacetal clearing agent by filtering the second reaction mixture and drying the filtered second reaction mixture.

More specifically, this method includes the following steps.
(A) A step of obtaining a first reaction mixture by mixing an aromatic aldehyde, a polyol, and an acid catalyst in an organic polar solvent. The equivalent ratio of the aromatic aldehyde to the polyol is 2: 1 to 2: 2.
(B1) obtaining a precipitate by adding a hydrogenating agent to the first reaction mixture; The equivalent ratio of the hydrogenating agent to the aromatic aldehyde is 0.01: 1 or less.
(B2) A step of obtaining a second reaction mixture by adding an inorganic silicon-containing agent to the precipitate. The inorganic silicon-containing agent has a pH value of 6 to 12, and the amount of the inorganic silicon-containing agent used is 0.02% to 3.5% by weight based on the amount of aromatic aldehyde.
(C) filtering the second reaction mixture to obtain a filtered second reaction mixture, drying the filtered second reaction mixture to obtain a solid mixture, and pulverizing the solid mixture to obtain a powder form Obtaining a diacetal clearing agent;

After milling process, the particle size distribution of the prepared powdery diacetal clarifying agents are those d ₉₇ satisfy the commercial product requirements of less than 45 micrometers. More preferably, prepared powdery diacetal clarifiers are those d ₉₇ of less than 30 microns, since dispersed sufficiently and uniformly in the polyolefin, it is possible to improve the transparency of the plastic products.

  Examples of the inorganic silicon-containing substance may be the following nine specific substances, but are not limited thereto.

1. CAS number 12736-96-8, for example, Minbloc ^(TM) HC-400 (Unimin, New Canaan, Connecticut; pH: 9.9). This is sodium suck potassium aluminosilicate median particle size of 2.8 .mu.m.

2. CAS No. 13983-17-0 or CAS No. 7699-41-4, for example, wollastonite NYAD ^(R) 5000 (NYCO Minerals, Calgary, Alberta, Canada; pH: 9.9,10% aqueous suspension) . This is calcium silicate (chemical formula: CaSiO ₃ ) and wollastonite with a median particle size of 2.2 microns.

3. CAS No. 1327-39-5, for example Silton ^{(registered trademark)} JC30, (Mizusawa Industrial Chemicals, Tokyo, Japan; pH: 7~9). This is calcium sodium aluminosilicate with a median particle size of 3 μm.

4). CAS No. 1344-00-9, for example, Tixolex ^{(registered trademark)} 17 (Solvay), pH value: 9.5 to 10.5 (5% aqueous suspension), or, Sipernat ^(R) 44 ms (Evonik, Degussa, Essen, Germany), pH value: 11.5 (10% aqueous suspension). Tixolex ^(TM) 17, a median particle size of sodium aluminosilicate of 5 to 7 .mu.m. Sipernat ^(R) 44 ms is a sodium aluminosilicate having a median particle size of 3.5 [mu] m.

  5. CAS number 12001-26-2, for example, Susorite Mica 400-HK (Kings Mountain Minerals / Zemex Industrial Minerals, Atlanta, GA), that is, a mica having a pH value of 9.2. This is a potassium magnesium aluminosilicate with a median particle size of 15 μm.

  6). CAS number 57455-37-5, for example C.I. I. Pigment Blue 29 (pH: 6-9), or Ultramarine Blue N-1200, Ultramarine Blue No. 2000, Ultramarine Blue N-2041, Ultramarine Blue N-2350, or Ultramarine Blue N-3152 (pH: 8.5 to 10.5, Daiichi Kasei Kogyo, Japan; pH: 8.5 to 10.5) . It is a natural or synthetic inorganic pigment, ie sodium aluminosilicate containing a trisulfur radical anion (S3).

7). CAS number 1344-01-0, for example, Silon ^{(registered trademark)} JC50, (Mizusawa Chemical, Tokyo, Japan; pH: 7-9). This is calcium sodium aluminosilicate with a median particle size of 5 μm.

8). CAS No. 1318-93-0, Cloisite ^{(R) Na} + (Southern Clay Products, Gonzales, TX; pH: 9.0 (2% aqueous suspension)), NSP103 (nano-silicate plates, JJ nanotechnology stock Company; pH: 9 to 10 (1 wt% aqueous suspension)). Cloisite ^{(registered trademark)} Na ⁺ is "(Al _1.33-1.67 Mg _0.33-0.67 ) (Ca _0-1 Na _0-1 ) _0.33 Si ₄ (OH) ₂ O ₁₀ . It is a modified montmorillonite or a hydrated aluminosilicate represented by the chemical formula “xH ₂ O”. NSP103 is an aqueous suspension of exfoliated montmorillonite silica nanomaterial having a median particle size of less than 1 micrometer (see Patent Document 12).

9. CAS No. 227605-22-3, e.g., Laponite ^(R) RD (Southern Clay Products; pH : 9~10 (2% aqueous suspension), median particle size of less than 50 nm, lithium magnesium sodium oxide silicate Chemical formula: Li _0.03 Mg _0.39 Na _0.07 O _0.15 (Si ₂ O ₅ ) _0.28 ).

  Preferably, the inorganic silicon-containing agent is at least one inorganic silicon-containing fine powder or aqueous suspension having a pH value of 8 to 10 and a median particle size of 10 μm or less.

  According to the invention, it is preferred that the equivalent ratio of aromatic aldehyde to polyol is from 2: 1.05 to 2: 1.3. The equivalent ratio of hydrogenating agent to aromatic aldehyde is preferably 0.03: 1 to 0.3: 1.

  Preferably, the amount of the inorganic silicon-containing agent is 0.2% to 1.0% by weight based on the amount of aromatic aldehyde.

  Preferably, the aromatic aldehyde applicable to the present invention may be a thiophene carboxaldehyde-based compound, a benzaldehyde-based compound, or a combination thereof. The thiophene carboxaldehyde-based compound may be unsubstituted thiophene carboxaldehyde or a substituted thiophene carboxaldehyde having 1 to 3 substituents. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms, and fluorine, chlorine, bromine, and the like. Selected from the group consisting of For example, the thiophene carboxaldehyde-based compound may be 5-methyl-2-thiophene carboxaldehyde. The benzaldehyde-based compound may be unsubstituted benzaldehyde or a substituted benzaldehyde having 1 to 3 substituents. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms, and fluorine, chlorine, bromine, and the like. Selected from the group consisting of For example, the benzaldehyde may be, but is not limited to, 4-methylbenzaldehyde, 4-n-butylbenzaldehyde, or 3,4-dimethylbenzaldehyde.

  Preferably, the acid catalyst applicable to the present invention may be sulfuric acid, phosphoric acid, hydrochloric acid, methanesulfonic acid, camphorsulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, or any combination thereof.

  Preferably, the organic polar solvent applicable to the present invention may be methanol, ethanol, dimethylformamide, acetonitrile, water, or any combination thereof, but is not limited thereto. According to the present invention, the solution used to mix with the precipitated product may be methanol, but is not limited thereto. According to the present invention, undesirable reactants, intermediates and impurities can be dissolved in the solution, and the desired diacetal can be precipitated under mild conditions. Reactants, intermediates and impurities can be removed from the high purity final product, i.e., powdered diacetal clearing agent, easily and safely through filtration and washing steps. Therefore, it can be seen that the above-described method for producing the powdered diacetal clearing agent is much simpler and safer than the conventional method.

Preferably, the hydrogenating agent applicable to the present invention is sodium hydride (NaH), potassium hydride (KH), aluminum hydride (AlH ₃ ), sodium cyanoborohydride (NaBH ₃ (CN)), hydrogen diisobutylaluminum hydride _{([(i-C 4 H} 9) 2 AlH] 2), lithium borohydride (LiBH _4), hydrogenated sodium borohydride (NaBH _4), potassium borohydride _(KBH 4), calcium borohydride ( Ca (BH ₄ ) ₂ ) or any combination thereof may be used. More preferably, the hydrogenating agent may be sodium borohydride or potassium borohydride.

  More preferably, the hydrogenating agent is sodium borohydride or potassium borohydride. Therefore, by using the hydrogenating agent to react with an aromatic aldehyde, the process safety of the powdered diacetal clearing agent can be ensured.

Here, the hydrogenating agent may be in powder, tablet or liquid form which is supplied for mixing with the first reaction mixture. Commercial hydrogenation agents include VenPure ^™ AF (high purity sodium borohydride tablets), VenPure ^™ SF (high purity sodium borohydride powder), VenPure ^™ solution (concentration adjustable sodium hydroxide and sodium borohydride. Solution) or VenPure ^™ K (high purity potassium borohydride powder).

  Therefore, depending on the method for producing the powdery diacetal clearing agent described above, by reacting the first reaction mixture with an appropriate hydrogenating agent, the malodor remaining in the first reaction mixture is released, and the heat stable. Undesirable substances that have low properties can be made into low odor, easily purified substances. In addition, by mixing a specific inorganic silicon-containing agent and a precipitate, the powdered diacetal clearing agent is substantially free of impurities, does not emit malodor, has high heat resistance, and is easily filtered and dried. It becomes something that can be manufactured through.

  Preferably, the method according to the present invention produces a high-purity powdered diacetal clearing agent having a purity of 98.5% or more as measured by high performance liquid chromatography (HPLC) and an aromatic aldehyde (impurity) of less than 50 ppm. Can be provided. Here, the purity of the powdered diacetal clearing agent is measured by high performance liquid chromatography, and the residue of the aromatic aldehyde is measured by gas chromatography (GC). More preferably, the prepared powdery diacetal clearing agent is purified by high performance liquid chromatography to a purity of 99% or more, and any aromatic aldehyde is not detected.

  The present invention also provides a plastic composition having good heat resistance and a low yellowness index comprising the powdered diacetal clearing agent described above and a polyolefin material.

  Preferably, the amount of the high purity powdered diacetal clearing agent is 0.05 wt% to 0.5 wt% based on the total amount of the plastic composition. Preferably, the amount of the high purity powdered diacetal clearing agent is 0.1% to 0.3% by weight based on the total amount of the plastic composition.

  The polyolefin material applicable to the present invention has a crystallinity of 5% to 100%. Preferably, the polyolefin material is a crystalline resin having a crystallinity of 95% and 15%, such as a polyethylene resin, a polypropylene resin, and a polybutylene resin. The catalyst used for preparing the polymer is not particularly limited. Conventional catalysts exist such as radical polymerization catalysts, Ziegler-Natta catalysts, magnesium halide supported transition metal catalysts, metallocene catalysts, and catalysts in combination with alkylaluminum compounds, triethylaluminum, or chlorodiethylarman.

  The polyethylene resin may be a high density polyethylene, a medium density polyethylene, a low density polyethylene, a linear low density polyethylene, or an ethylene copolymer containing 50% by weight or more of ethylene. The polypropylene resin may be a polypropylene homopolymer or a propylene copolymer containing 50% by weight or more of propylene. The polybutylene resin may be a polybutylene homopolymer or a polybutylene copolymer containing 50% by weight or more of polybutylene. The copolymer may be a random copolymer or a block copolymer. The stereoregularity of the resin may be a cis type or a trans type.

  For example, α-olefins such as ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, and dodecane may be used. For example, a copolymer of a dicyclomonomer such as 1,4-bicyclo [2.2.1] hepta-2,5-diene, a methyl acrylate monomer such as methyl methacrylate or methyl ethyl acrylate, ethyl acetate, and maleic acid It can be applied as a monomer.

  Powdered diacetal clearing agents having a low yellowness index can be mixed with various plastic additives having different functions formed into powders, granules, tablets, and bars. For examples of plastic additives, reference can be made to the plastic additive handbook 5th edition. For example, the additive is pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (trade names: Irganox 1010, K-NOX1010), 1,3,5- Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (trade name: Irganox 1330, K-NOX 230), tris (2,4-di-tert) -Butylphenyl) phosphite (trade name: Irgaphos 168, K-NOX168), 3,9-bis (2,4-di-tert-butylphenoxy) -2,4,8,10 tetraoxa-3,9-di -Phosphaspiro [5.5] undecane (trade name: Irgaphos 126, K-NOX626), and calcium stearate It may be, but is not limited thereto.

Invention of Claim 1 of this application is a powdery diacetal transparent agent, Comprising: The diacetal compound selected from the group which consists of a compound represented by general formula (I)-(V),
Here, R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, 1 to 4 carbon atoms, fluoro, A substituent selected from the group consisting of an alkoxycarbonyl group having chloro and bromo, wherein a and b are each independently an integer selected from 0 to 3, and have a pH value of 6 or more and 12 or less A powdery diacetal clearing agent characterized by having an inorganic silicon-containing compound.

  The invention of claim 2 of the present application is characterized in that the amount of the inorganic silicon-containing compound is 0.02 wt% to 3.0 wt% based on the total amount of the powdery diacetal clearing agent. A powdery diacetal clearing agent according to claim 1 is provided.

  The invention according to claim 3 of the present application is characterized in that the amount of the inorganic silicon-containing compound is 0.2 wt% to 1.0 wt% based on the total amount of the powdery diacetal clearing agent. A powdery diacetal clearing agent according to 2, is provided.

  The invention according to claim 4 of the present application is characterized in that the diacetal compound is 1,3: 2,4-di (5-methyl-2-tenylidene) -D-sorbitol, 1,3: 2,4-di (4-methyl). Benzylidene) -D-sorbitol, 1,3: 2,4-di (4-n-butylbenzylidene) -D-sorbitol, and 1,3: 2,4-di (3,4-dimethylbenzylidene) -D- The powdery diacetal clearing agent according to claim 1, which is selected from the group consisting of sorbitol.

  The invention of claim 5 of the present application provides the powdery diacetal clearing agent according to claim 1, wherein the inorganic silicon-containing compound has a median particle size of 15 micrometers or less.

  The invention of claim 6 of the present application is that the inorganic silicon-containing compound is sodium, potassium, aluminosilicate, calcium silicate, sodium, calcium aluminosilicate, sodium aluminosilicate, potassium, magnesium, aluminosilicate, hydrated aluminosilicate. The powdery diacetal clearing agent according to claim 5, wherein the powdered diacetal clearing agent is selected from the group consisting of lithium, magnesium, sodium oxide, silicic acid, and any combination thereof.

  The invention of claim 7 of the present application is characterized in that the inorganic silicon-containing compound has a pH value of 8 or more and 10 or less, and the median particle size of the inorganic silicon-containing compound is 10 micrometers or less. The powdery diacetal clearing agent according to claim 5 is provided.

  The invention according to claim 8 of the present application provides the powdery diacetal clearing agent according to claim 7, wherein the inorganic silicon-containing compound is sodium aluminosilicate containing a trisulfur radical anion.

  The invention of claim 9 of the present application is that the inorganic silicon-containing compound is a nanomaterial of exfoliated montmorillonite silica having a median particle size of less than 1 micrometer, and the pH value of the nanomaterial of exfoliated montmorillonite silica is 9 The powdery diacetal clearing agent according to claim 5 is provided.

  The invention of claim 10 of the present application is that the inorganic silicon-containing compound is lithium magnesium oxide sodium silicate having a median particle size of less than 50 nanometers, and the pH value of the lithium magnesium oxide sodium silicate is 9-10. The powdery diacetal clearing agent according to claim 5 is provided.

  Invention of Claim 11 of this application is a manufacturing method of a powdery diacetal transparent agent, Comprising: (a) Aromatic aldehyde, a polyol, and an acid catalyst are mixed in an organic polar solvent, A 1st reaction mixture The equivalent ratio of the aromatic aldehyde to the polyol is 2: 1 to 2: 2, and (b) adding a hydrogenating agent and an inorganic silicon-containing agent to the first reaction mixture, Obtaining a second reaction mixture, wherein the equivalent ratio of the hydrogenating agent to the aromatic aldehyde is greater than 0.01: 1, the inorganic silicon-containing agent has a pH value of 6-12, and the inorganic silicon The use amount of the content agent is 0.02 wt% to 3.5 wt% based on the amount of the aromatic aldehyde, and (c) when the second reaction mixture is filtered. To, by drying the filtered said second reaction mixture, to provide a method for manufacturing a powdery diacetal transparent agent characterized by having a step of obtaining a powdery diacetal clarifiers.

  The invention according to claim 12 of the present application is the powdery diacetal clearing agent according to claim 11, wherein the equivalent ratio of the polyol to the aromatic aldehyde is from 2: 1.05 to 2: 1.3. A manufacturing method is provided.

  The invention according to claim 13 of the present application is characterized in that the equivalent ratio of the hydrogenating agent to the aromatic aldehyde is 0.03: 1 to 0.3: 1, A method for producing an agent is provided.

  The invention according to claim 14 of the present application is characterized in that the amount of the inorganic silicon-containing agent is 0.2 wt% to 1.0 wt% based on the amount of the aromatic aldehyde. A method for producing the described powdery diacetal clearing agent is provided.

  The invention according to claim 15 of the present application is characterized in that the aromatic aldehyde is a thiophenecarboxaldehyde compound, a benzaldehyde compound, or a combination thereof, The method for producing a powdery diacetal transparent agent according to claim 11 I will provide a.

  The invention according to claim 16 of the present application is that the thiophenecarboxaldehyde-based compound is unsubstituted thiophenecarboxaldehyde or thiophenecarboxaldehyde having 1 to 3 substituents, and the substituent is 1 to 4 carbon atoms. And a substituent selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms, fluoro, chloro, and bromo. A method for producing a powdery diacetal clearing agent according to claim 15 is provided.

  The invention of claim 17 of the present application provides the method for producing a powdery diacetal clearing agent according to claim 11, wherein the aromatic aldehyde is 5-methyl-2-thiophenecarboxaldehyde.

  In the invention of claim 18 of the present application, the benzaldehyde-based compound is an unsubstituted benzaldehyde or a benzaldehyde having 1 to 3 substituents, and the substituent is an alkyl group having 1 to 4 carbon atoms, 1 16. A substituent selected from the group consisting of an alkoxy group having 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms, fluoro, chloro, and bromo. A method for producing the described powdery diacetal clearing agent is provided.

  The invention of claim 19 of the present application is characterized in that the aromatic aldehyde is selected from the group consisting of 4-methylbenzaldehyde, 4-n-butylbenzaldehyde, and 3,4-dimethylbenzaldehyde. A method for producing a powdery diacetal clearing agent according to claim 11, is provided.

  According to the invention of claim 20 of the present application, the hydrogenating agent is sodium hydride, potassium hydride, aluminum hydride, sodium cyanoborohydride, diisobutylaluminum hydride, lithium borohydride, sodium borohydride, hydrogenation. The method for producing a powdery diacetal clearing agent according to claim 11, wherein the method is potassium borohydride, calcium, borohydride, or any combination thereof.

  The invention of claim 21 of the present application provides the method for producing a powdery diacetal transparent agent according to claim 20, wherein the hydrogenating agent is sodium borohydride or potassium borohydride.

  The present invention improves powdered diacetal clearing agents, and in plastic products made using powdered diacetal clearing agents, low yellowness index, simple operation, and good heat resistance, during the plastic processing process Prevention of malodor, good tolerance to withstand high temperatures when mixing plastic raw materials, good color stability in final plastic products made with powdered diacetal clearing agent, transparent appearance and powdery Technical effects such as improved visual properties of final plastic products made using diacetal clearing agents can be provided.

It is an electron microscope image of the powder diacetal clearing agent of Example 4 according to the present invention at a magnification of 2000 ×. It is an electron microscope image of the powder diacetal clearing agent of the comparative example 2 which concerns on this invention in the magnification of 2000X. It is an electron microscope image of a commercial item (GENISET ^{(registered trademark)} DXR) at a magnification of 2000X. It is an electron microscope image of the powdery diacetal clearing agent of Example 4 which concerns on this invention in the magnification of 5000X. It is an electron microscope image of the powder diacetal clearing agent of the comparative example 2 which concerns on this invention in the magnification of 5000X. It is an electron microscope image of the commercial item (GENISET ^(trademark) DXR) in the magnification of 5000X. It is a graph which shows the powder flow function of the powdery diacetal clearing agent of Example 4 according to this invention and the comparative example 2. FIG.

  Preferred embodiments of the present invention will be described below in detail with reference to the accompanying drawings.

The following examples are provided so that those skilled in the art can easily realize the advantages and effects of the present invention.
It should be understood that the embodiments disclosed herein are not intended to limit the scope of the invention, but are exemplary and are preferred examples provided only for the description of the invention. Modifications and changes may be made to implement or apply the invention without departing from the spirit and scope of the invention.

  Examples 1 to 8 and Comparative Examples 1 to 3 are described as follows in order to explain the raw materials, detection methods, and conditions regarding the powdery diacetal clearing agent.

1. Yield The theoretical mass of the powdered diacetal clearing agent is determined based on the aromatic aldehyde that is to be defined as the reagent. The actual mass of the purified and dried product is divided by the theoretical mass and then multiplied by 100% to determine the yield.

2. Melting point (Tm) and crystallization temperature (Tc)
The powdery diacetal clearing agents according to Examples 1 to 8 and Comparative Examples 1 to 3 were measured with a differential scanning calorimeter thermal analyzer (Mettler Toledo ^{(registered trademark)} , DSC821e). “Mettler Toledo” is a registered trademark of METTLER TOLEDO. Samples are heated from room temperature to 290 ° C. at a heating rate of 10 ° C. per minute and their melting point and crystallization temperature (also called nucleation temperature) are recorded.

3. Fourier transform infrared spectroscopy (FTIR)
During the experiment, each sample is mixed with potassium bromide (KBr) at a weight ratio of 1:50 to 1: 100, completely ground, and then subjected to a pressing process to obtain an extruded sample. FTIR spectra are determined Thermo Nicolet range of ^(TM) 330ft-IR spectrometer ^{4000cm -1 ~400cm} -1, the characteristic functional groups of samples. “Nicolet” and “Thermo Nicolet” are registered trademarks of Thermo Nicolet Corporation.

4). Proton nuclear magnetic resonance spectroscopy ( ¹ H-NMR)
Each sample, after being dissolved in deuterated dimethyl sulfoxide _{(DMSO-d 6),} make measurements at 400MHz with Varian ^(TM) NMR-400 spectrometer. “Varian” is a registered trademark of Varian.

  Measurement data were reported as chemical shifts (multiplicity, number of hydrogen atoms). Chemical shifts labeled “δ” were reported in ppm. For multiplicity, “s” represents a single, “d” represents a doublet, “t” represents a triplet, “dd” represents a doublet of a doublet, and “td” represents a doublet. “M” represents a multiplet, and “br” represents a broadband.

5. Absorbance (ABS)
Each sample was dissolved in dimethyl sulfoxide to obtain a 1000 ppm solution, and then measured using a UV / VIS spectrophotometer (JASCO, JASCO V-550) to measure the absorbance of the absorption peak. .

6). Ash content In order to determine the ash content contained in the powdered diacetal clearing agents of Examples 1 to 8 and Comparative Examples 1 to 3, an accurately weighed 1 g sample was placed in a heating furnace with an initial weight of W0 and 600 ± After heating to 25 ° C. for 3 hours, the color of the sample was observed.
The sample is then returned to the furnace and heated to 800 ± 25 ° C. for 2 hours, and when the carbon is completely burned out, white gray ash is obtained. Subsequently, the white gray ash was transferred to a dryer cabinet, cooled to room temperature, weighed, and the residue weight was recorded as W1. The ash content was calculated by the following formula.

7). Purity determined by liquid chromatography (LC) Waters ^(R) 2487 liquid chromatography (LC) fitted with a LiChrosphere ^(R) 100 column RP-18 was used. The column has a 25 centimeter long, 4 millimeter inner diameter, 5 micrometer thick film and an outer temperature of 30 ° C.
A mixture of LC grade acetonitrile and water (V / V: 650/350) used as the eluting solvent is run over the column at 0.8 ml / min. The sample concentration is 1000 ppm by dissolving the sample powder in dimethylformamide and diluting with methanol. Each injection amount is 20 microliters. “Waters” and “LiChrosphere” are registered trademarks of Waters and Merck, respectively.

The wavelength and retention time of the UV radiation varies between the various compounds and is described as follows.
1,3: 2,4-di (5-methyl-2-tenylidene) -D-sorbitol: 254 nm, 3.32 min.
1,3: 2,4-di (4-methylbenzylidene) -D-sorbitol: 254 nm, 4.93 min.
1,3: 2,4-di (3,4-dimethylbenzylidene) -D-sorbitol: 254 nm, 6.24 minutes.
1,3: 2,4-di (4-n-butylbenzylidene) -D-sorbitol: 254 nm, 21.32 minutes.
Depending on the different LC instruments and the shift in the number of column theoretical plates, the aforementioned retention times vary slightly.

8). SHIMADZU having a residual J & W column HP-1 aromatic aldehyde ^(TM) Gas chromatography GC-2014 was used. The column has a length of 30 meters, a diameter of 0.32 centimeters, and a film thickness of 0.25 micrometers. The injection temperature was set at 200 ° C and the detection temperature was set at 280 ° C. The column performs measurement at a flow rate of 2 ml per minute using helium gas as a carrier gas. The split ratio is 10: 1. During the experiment, the column temperature was heated at a heating rate of 15 ° C. per minute, initially set at 100 ° C. for 3 minutes, and finally held at 230 ° C. for 9 minutes. “Shimadzu” is a registered trademark of Shimadzu Corporation.

Retention times are different for various aromatic aldehydes as follows.
5-Methyl-2-thiophenecarboxaldehyde: 5.23 minutes.
4-Methylbenzaldehyde: 4.83 minutes.
3,4-dimethylbenzaldehyde: 6.51 minutes.
4-n-butylbenzaldehyde: 6.32 minutes.
Depending on the different GC instruments and the shift in the number of column theoretical plates, the aforementioned retention times will vary slightly.

  In the experiment, 1 g of a different sample of powdered diacetal clearing agent was dissolved in 10 ml of methanol and then sonicated for 30 minutes to obtain a mixture. After filtering the mixture, the filtrate was collected to determine the amount of aromatic aldehyde. When the absorption peak of aromatic aldehyde was not confirmed, the result was described as “not detected”. Here, the detection limit of the instrument was 1 ppm, and the detection limit of the sample was 10 ppm.

9. Yellowness index (YI)
The HunterLab ColorFlex ^(TM) EZ colorimeter was used to measure the YI. Each sample is measured three times to obtain an average value as the YI of the sample. “ColorFlex” is available from Hunter Associates Laboratory, Inc. Is a registered trademark.

  A high positive YI was a representation that the appearance of the sample was yellow, and a low negative YI was that the appearance of the sample was blue. A YI close to zero gave the sample almost white.

10. The particle size of the particle size powdered diacetal transparent agent was measured by Beckman Coulter ^(R) LS 13 320 / ISO 13320 laser diffraction particle size analyzer with a trace module. “Beckman Coulter” is a registered trademark of Beckman Coulter.

Each sample of 15 mg is dispersed in ethanol to obtain 100 ml of solution. 1 minute After sonication the solution, the solution is injected into the cell of trace module and reaches the 10% coverage, as measured article of the laser particle size analysis, particle size of 97% of the particles from d ₉₇ Record small particle size and median particle size. Each sample is measured three times to obtain an average value.

11. Specification of aromatic aldehyde i, 5-methyl-2-thiophenecarboxaldehyde (SIGMA-ALDRICH, CAS number 13679-70-4, purity: 98%).
ii, 4-methylbenzaldehyde (manufactured by Mitsubishi Gas Chemical Company, trade name: PTAL, purity> 99%).
iii, 3,4-dimethylbenzaldehyde (manufactured by Mitsubishi Gas Chemical Company, trade name: 3,4-DBAL, purity> 99%).
iv, 4-n-butylbenzaldehyde (manufactured by Mitsubishi Gas Chemical Company, trade name: NBBAL, purity> 98%).
v, vs. D-sorbitol (Shijiazhuang Ruixue Pharmaceutical Co., Ltd., China, purity> 99%).

12. Specification of commercially available polyolefin i, Globalene ST611: General polypropylene random copolymer, manufactured by Taiwan LCY Chemical Industry Co., Ltd., Melt Flow Index (230 ° C., 2.16 kg): 1.8 g per 10 minutes.
ii, Tairipro T3002: Blow molding grade polypropylene random copolymer, manufactured by Formosa Chemicals & Fibers Co., Ltd., melt flow index (230 ° C., 2.16 kg): 1.6 g per 10 minutes.
iii, Basell Moplen RP242G (Lyondell Basell Industries): low melt flow index, chemical and resistant grade polypropylene random copolymer, made by HMC polymer (Thailand), melt flow index (230 ° C., 2.16 Kg): 0 per 10 minutes .15 g.
iv, Borealis RB307MO: Blow molding grade polypropylene random copolymer, manufactured by Borealis, melt flow index (230 ° C., 2.16 Kg): 1.5 g per 10 minutes.
v, Titanpro SM198: blow molding grade polypropylene random copolymer, manufactured by Titan Chemicals (Bhd), melt flow index (230 ° C., 2.16 Kg): 1.6 g per 10 minutes.
vi, Engage 8480: ethylene-octene copolymer, manufactured by Dow Chemical Co., melt flow index (190 ° C, 2.16 Kg): 1 g per 10 minutes.

13. Diacetal clarifying agent product i for comparison, 1,3: 2,4-di (4-methylbenzylidene)-D-sorbitol (MDBS), for example, Millad commercial products Milliken Chemical Co. ^{(registered trademark)} 3940, Or, a commercial product LM30 manufactured by Shin Nippon Chemical Co., Ltd.
ii, 1, 3: 2,4-di (3,4-dimethyl benzylidene)-D-sorbitol (DMDBS), for example, Milliken Chemical Company commercial product Millad ^(TM) 3988I or Rita Corporation commercial, goods Geniset ^{(registered trademark)} DXR.

<Example 1>
In this example, 1,3: 2,4-di (5-methyl-2-tenylidene) -D-sorbitol was prepared by the following procedure as a powdery diacetal clearing agent.
(A) In a 500 ml four-necked cylindrical reaction flask equipped with a thermometer, nitrogen inlet, and mechanical stirrer, D-sorbitol (19.0 g, 0.104 mol), methanesulfonic acid (0.4 g), 5-Methyl-2-thiophenecarboxaldehyde (25.0 g, 0.198 mol) and methanol (150 g) were charged and allowed to react at room temperature for 45 hours to form a first reaction mixture.
(B) The first reaction mixture is filtered to remove the mother liquor, and 100 g of methanol and 10% sodium hydroxide solution are slowly added to the reaction flask to neutralize the solution to pH> 7. Thereafter, potassium borohydride powder (0.3 g, purity> 96%) and ultramarine blue (0.15 g, CAS number 57455-37-5) were added to the first reaction mixture and stirred for 1 hour, A second reaction solution is obtained.
(C) Filter the second reaction solution and collect a solid precipitate from the second reaction solution. Next, the solid precipitate was washed with a 40% by weight methanol solution, dried, and pulverized, whereby 1,3: 2,4-di (5- Methyl-2-tenylidene) -D-sorbitol (28.4 g, yield 72.1% (calculated from 39.4 g of theoretical mass)) is obtained. Based on the total weight of the powdered diacetal clearing agent, the amount of ultramarine blue is about 0.5% by weight.

The powdery diacetal clearing agent according to Example 1 has the following characteristics.
i, melting point: 198.78 ° C.
ii, ¹ H-NMR spectrum (400 MHz, d ₆ -DMSO): δ 6.89 (d, 2H), 6.69 (d, 2H), 5.79 (s, 2H), 4.79 (d, 1H) ), 4.41 (t, 1H), 4.17 to 4.00 (m, 3H), 3.88 (s, 1H), 3.80 to 3.78 (m, 1H), 3.75 to 3.65 (m, 1H), 3.60 to 3.55 (m, 1H), 3.50 to 3.40 (m, 1H), 2.42 (s, 6H).
iii, FTIR spectrum data (infrared spectroscopy analysis cm ⁻¹ ): λ3222, 2918, 2866, 1497, 1449, 1398, 1371, 1341, 1266, 1227, 1164, 1133, 1110, 1081, 1167, 1021, 1000, 960 , 884, 858, 802, 769, 667, 614, 570, 544, 486 cm ⁻¹ .
iv, UV / VIS spectral data: 262 nm absorbance: 2.1820; 292 nm absorbance: 1.0658; 649 nm absorbance: 0.0036.
v, Ash content: 0.51%.
Vi, purity by LC: 99.6%.
vii, GC analysis result of residue of aromatic aldehyde: 5-methyl-2-thiophenecarboxaldehyde is not detected.

<Comparative Example 1>
Conventional clearing agent composition comprising 1,3: 2,4-di (5-methyl-2-tenylidene) -D-sorbitol and organosilane-treated fume silica as described in Example 4 of Patent Document 13 Was prepared as follows.
(A) In a 1 L four-necked cylindrical reaction flask equipped with a thermometer, nitrogen inlet, and mechanical stirrer, D-sorbitol (20.0 g, 0.110 mol), methanesulfonic acid (1.00 g), 5-Methyl-2-thiophenecarboxaldehyde (25.0 g, 0.198 mol) and methanol (200 ml) were charged and reacted for 48 hours at room temperature to form a first reaction mixture.
(B) The first reaction mixture was neutralized with 4% of sodium hydroxide solution to pH 8-9 and organosilane treated silica fume (3.0 g, CAB-O-SIL® TS-720 ^). ) To form a second reaction mixture.
(C) Filter the second reaction mixture and collect the precipitate. The precipitate is then washed with 40% of the methanol solution, dried, crushed and 1,3: 2,4-di (5-methyl-2-tenylidene) -D-sorbitol exhibiting a pale yellow color on white (30.7 g) is obtained.

The resulting product has the following characteristics.
i, melting point: 212.5 ° C.
ii, FTIR spectrum data (infrared spectroscopic analysis cm ⁻¹ ): λ3287, 2919, 1678, 1498, 1457, 1398, 1377, 1341, 1265, 1226, 1164, 1081, 1056, 1021, 960, 894, 802, 769 , 671, 644, 614, 584, 485 cm ⁻¹ .
iii, ash: 9.2%.
iv, purity by LC: 93.70%.

<Example 2>
In this example, 1,3: 2,4-di (3,4-dimethylbenzylidene) -D-sorbitol was prepared by the following procedure as a powdery diacetal clearing agent.
(A) In an 80 L small reaction flask equipped with a thermometer, a nitrogen inlet, and a mechanical stirrer, D-sorbitol (4000 g, 22 mol), methanesulfonic acid (100 g), 3,4-dimethylbenzaldehyde (5300 g, 39.5 moles), and methanol (40 L) were charged and reacted at room temperature for 42 hours to form a first reaction mixture.
(B) The first reaction mixture was filtered to remove the mother liquor, and 20 L of methanol was newly added. Thereafter, 12% potassium borohydride solution (200 g) and ultramarine blue (1.28 g) are slowly added to the first reaction mixture and stirred for 1 hour to obtain a second reaction solution.
(C) Filter the second reaction solution and collect a solid precipitate from the second reaction solution. The solid precipitate is then washed with 40% by weight methanol solution and dried as a powdered diacetal clearing agent, giving a white color, 1,3: 2,4-di (3,4-dimethylbenzylidene) -D -Sorbitol (6613 g, yield 80.8% (calculated from 8185 g of theoretical mass)) is obtained. Based on the total weight of the powdered diacetal clearing agent, the amount of ultramarine blue is about 0.02% by weight.

The powdery diacetal clearing agent according to Example 2 has the following characteristics.
i, melting point: 274.45 ° C., crystallization temperature: 227.99 ° C.
ii, ¹ H-NMR spectrum (400 MHz, d ₆ -DMSO): δ 7.23-7.11 (m, 6H), 5.58 (s, 2H), 4.81 (d, 1H), 4.41 (T, 1H), 4.14 to 4.09 (m, 3H), 3.88 (s, 1H), 3.81 to 3.74 (m, 2H), 3.65 to 3.57 (m 1H), 3.50 to 3.40 (m, 1H), 2.24 (s, 12H).
iii, FTIR spectrum data (infrared spectroscopic analysis cm ⁻¹ ): λ3212, 2939, 2858, 1505, 1453, 1400, 1372, 1340, 1262, 1245, 1213, 1168, 1125, 1098, 1068, 1026, 998, 898 881, 857, 824, 790, 769, 714, 668, 632, 578, 543, 475, 436 cm ⁻¹ .
iv, UV / VIS spectral data: 265 nm absorbance: 1.5606; 649 nm absorbance: 0.0007.
v, Ash content: 0.01%.
Vi, purity by LC: 99.75%.
vii, GC analysis result of aromatic aldehyde residue: 3,4-dimethylbenzaldehyde was not detected.

<Examples 3 to 6>
1,3: 2,4-di (3,4-dimethylbenzylidene) -D-sorbitol used as a powdery diacetal clearing agent according to Examples 3 to 6 was prepared by the method described in Example 2. It has been done.
The difference between Example 3 and Example 6 is that different amounts of inorganic silicon-containing agent were used in different amounts. That is, in Examples 3 to 5, Ultramarine Blue (CAS No. 57455-37-5) was used as the inorganic silicon-containing agent, whereas in Example 6, Tixolex ^{(registered trademark)} 17 (CAS number 1344-00-9) is used as the inorganic silicon-containing agent. Table 1 shows the amounts of powdered diacetal clearing agents used in Examples 3 to 6. None of the white powdery diacetal clearing agents according to Examples 3 to 6 emitted a bad odor, and none of them detected 3,4-dimethylbenzaldehyde.

  Table 1 lists properties such as observation yield, melting point, crystallization temperature, ash content, and absorbance from the UV / VIS spectrum obtained by the detection method as described above.

Further, commercially available products Millad ^(TM) 3988I and Geniset ^{(registered trademark)} DXR, i.e., no ultramarine blue 1,3: 2,4-di (3,4-dimethyl benzylidene)-D-sorbitol, comparative The properties are listed in Table 1 below.

Table 1: Amount of inorganic silicon-containing substance (unit: g), yield (unit:%), ash (unit:%), melting point (Tm, unit: ° C) and crystallization temperature (Tc, unit: C ° ) as measured by a thermal analysis apparatus differential scanning calorimeter, the absorbance at 265nm and 649nm from 262 (ABS) is, Millad which was obtained from UV / VIS spectra 6 example 3 commercially available ^(R) 3988I and Geniset ^{( (Registered trademark)} DXR.

In addition to the characteristics shown in Table 1 above, other analysis results of the powdery diacetal clearing agents of Examples 3 to 6 are listed as follows.
I, analysis results of Example i i, purity by LC: 99.69%.
ii, FTIR spectrum data: λ3212, 3014, 2939, 2858, 1505, 1452, 1400, 1371, 1339, 1308, 1262, 1245, 1213, 1168, 1126, 1097, 1058, 1026, 997, 898, 881, 857 , 824, 790, 769, 713, 668, 632, 578, 543, 436 cm ⁻¹ .
iii, based on the total weight of the powdered diacetal clearing agent, the amount of ultramarine blue is 0.2% by weight.

II, Analytical result of Example 4 i, Purity by LC: 99.66%.
ii, FTIR spectrum data: λ3213, 2939, 2859, 1505, 1453, 1400, 1371, 1340, 1262, 1247, 1213, 1168, 1125, 1098, 1058, 1026, 998, 898, 881, 857, 824, 790 770, 668, 632, 578, 543, 436 cm ⁻¹ .
iii, based on the total weight of the powdered diacetal clearing agent, the amount of ultramarine blue is 0.5% by weight.

III, analysis results of Example 5 i, purity by LC: 99.69%.
ii, FTIR spectrum data: λ3216, 2939, 2859, 1619, 1505, 1453, 1400, 1371, 1340, 1261, 1246, 1212, 1168, 1125, 1098, 1057, 1026, 998, 898, 881, 858, 824 , 790, 770, 713, 669, 632, 579, 544, 437 cm ⁻¹ .
iii, based on the total weight of the powdered diacetal clearing agent, the amount of ultramarine blue is 1.0% by weight.

IV, Analytical results of Example 6 i, Purity by LC: 99.68%.
ii, FTIR spectrum data: λ3215, 2939, 2858, 1505, 1452, 1400, 1371, 1340, 1327, 1308, 1262, 1246, 1213, 1170, 1125, 1099, 1057, 1026, 998, 981, 899, 881 , 858, 824, 790, 770, 578, 543, 436 cm ⁻¹ .
iii, based on the total weight of the powdery diacetal transparent agent, the amount of Tixolex ^(TM) 17 is a 0.5% by weight.

<Comparative example 2>
In this example, 1,3: 2,4-di (3,4-dimethylbenzylidene) -D-sorbitol was prepared by the following procedure as a powdery diacetal clearing agent. In this comparative example, the hydrogenating agent and the inorganic silicon-containing agent were not used.
(A) To an 80 L small reaction flask equipped with a thermometer, a nitrogen inlet, and a mechanical stirrer, D-sorbitol (4000 g, 22 mol), methanesulfonic acid (100 g), 3,4-dimethylbenzaldehyde (5300 g, 39 .5 moles), and methanol (40 L) were charged and reacted for 42 hours at room temperature to form a first reaction mixture.
(B) The first reaction mixture is filtered to remove the mother liquor, and 30 L of methanol is newly added to the reaction flask and neutralized to a pH value of 8-9 with 4% sodium hydroxide solution. As a result, a mixed solution is obtained.
(C) The mixed solution is stirred for 1 hour and then filtered to obtain a precipitate. The precipitate is then washed with a 40 wt% methanol solution, dried as a powdered diacetal clearing agent and dried to give a white 1,3: 2,4-di (3,4-dimethylbenzylidene) -D- Sorbitol (6450 g, yield 78.8% (calculated from 8185 g of theoretical mass)) is obtained.

The powdery diacetal clearing agent according to Comparative Example 2 has the following characteristics.
i, melting point: 274.86 ° C., crystallization temperature: 227.47 ° C.
ii, FTIR spectrum data: λ3212, 3015, 2953, 2939, 2857, 1506, 1453, 1400, 1372, 1340, 1327, 1308, 1262, 1246, 1213, 1170, 1125, 1115, 1098, 1068, 1057, 1026 998, 981, 935, 899, 881, 858, 824, 790, 769, 713, 669, 632, 579, 543, 436 cm ⁻¹ .
iii, Ash: 0.01%.
iv, purity by LC: 98.62%.
v, Remaining amount of aromatic aldehyde measured by GC analysis: 120 ppm of 3,4-dimethylbenzaldehyde was detected.

<Example 7>
In this example, 1,3: 2,4-di (4-methylbenzylidene) -D-sorbitol was prepared by the following procedure as a powdery diacetal clearing agent.
(A) A 1 L four-necked cylindrical reaction flask equipped with a thermometer, nitrogen inlet, and mechanical stirrer was charged with D-sorbitol (56.78 g, 0.312 mol), camphorsulfonic acid (1.8 g). , 4-methylbenzaldehyde (68.1 g, 0.567 mol), methanol (500 g) were charged and allowed to react at room temperature for 40 hours to form a first reaction mixture.
(B) The first reaction mixture was filtered to remove the mother liquor, and 250 g of methanol was newly added and neutralized until the pH value reached 8 while stirring. Thereafter, potassium borohydride powder (1 g, purity> 96%) is added to the first reaction mixture was stirred for 30 minutes and then 4 wt% of Laponite ^(TM) RD of an aqueous suspension (10 g, CAS number 227605-22-3) was added and stirred for 1 hour to obtain a second reaction solution.
(C) The second reaction solution was filtered to collect the solid precipitate. The precipitate is then washed with 40% by weight methanol solution, dried and crushed to give 1,3: 2,4-di (4-methylbenzylidene) as a powdered diacetal clearing agent that exhibits an almost white powder. ) -D-sorbitol (86.5 g, yield 78.9% (calculated from 109.6 g of the theoretical mass)) was obtained. Based on the total weight of the powdery diacetal clarifiers, Laponite amount of ^(R) RD is about 0.46 wt%.

The powdery diacetal clearing agent according to Example 7 has the following characteristics.
i, melting point: 258.28 ° C, crystallization temperature: 202.41 ° C.
ii, ¹ H-NMR spectrum (400 MHz, d ₆ -DMSO): δ 7.34-7.30 (dd, 4H), 7.19-7.15 (dd, 4H), 5.59 (s, 2H) 4.81 (d, 1H), 4.39 (t, 1H), 4.20 to 4.09 (m, 3H), 3.88 (s, 1H), 3.81 to 3.78 (m) 1H), 3.75 to 3.70 (m, 1H), 3.59 to 3.54 (m, 1H), 3.42 to 3.38 (m, 1H), 2.28 (s, 6H) ).
iii, FTIR spectrum data: λ3222, 3031, 2956, 2862, 1619, 1517, 1450, 1400, 1371, 1342, 1328, 1312, 1264, 1168, 1098, 1057, 1022, 982, 944, 884, 835, 818 785, 778, 764, 661, 617, 599, 560, 543, 482 cm ⁻¹ .
iv, UV / VIS spectral data: 262 nm absorbance: 1.0152; 649 nm absorbance: 0.0048.
v, Ash content: 0.42%.
Vi, purity by LC: 99.27%.
vii, GC analysis result of aromatic aldehyde residue: 4-methylbenzaldehyde is not detected.

<Comparative Example 3>
As a powdery diacetal clearing agent, 1,3: 2,4-di (4-methylbenzylidene) -D-sorbitol was prepared using an acidic inorganic silicon-containing agent as a dispersant. The production of the powdery diacetal clearing agent has the following steps.
(A) A 1 L four-necked cylindrical reaction flask equipped with a thermometer, nitrogen inlet, and mechanical stirrer was charged with D-sorbitol (56.78 g, 0.312 mol), methanesulfonic acid (1.8 g), 4-Methylbenzaldehyde (68.1 g, 0.567 mol) and methanol (500 g) were charged and then allowed to react for 40 hours at room temperature to form a first reaction mixture.
(B) The first reaction mixture was filtered to remove the mother liquor, and 250 g of methanol was newly added and neutralized until the pH value reached 8 while stirring. Thereafter, sodium borohydride powder (0.5 g, purity> 96%) was added to the first reaction mixture and stirred for 30 minutes, then acid clay (trade name TONSIL® OPTIMUM 230FF; Clariant ⁾ ; pH A 10% aqueous suspension with a value of 2-3) was further added to form a second reaction solution.
(C) Filter the second reaction solution and collect a solid precipitate from the second reaction solution. Next, the solid precipitate was washed with a 40 wt% methanol solution, dried and pulverized to give an almost white powder as a powdered diacetal clearing agent and emit a slight aldehyde odor. : 2,4-di (4-methylbenzylidene) -D-sorbitol (85.3 g, yield 77.8% (calculated from 109.6 g of the theoretical mass)). Based on the total weight of the powdered diacetal clearing agent, the amount of acid clay is about 0.2% by weight.

The powdery diacetal clearing agent according to Comparative Example 3 has the following characteristics.
i, FTIR spectrum data: λ3221, 2956, 2941, 2862, 1619, 1517, 1450, 1400, 1371, 1342, 1328, 1311, 1264, 1226, 1168, 1133, 1098, 1056, 1022, 982, 944, 884 , 835, 818, 785, 764, 715, 661, 616, 599, 560, 543, 515, 482, 431 cm ⁻¹ .
ii, UV / VIS spectral data: 262 nm absorbance: 1.1494; 649 nm absorbance: 0.0787.
iii, ash: 2.35%.
iv, purity by LC: 94.65%.
v, GC analysis result of aromatic aldehyde residue: 4-methylbenzaldehyde is not detected.

<Example 8>
In this example, 1,3: 2,4-di (4-n-butylbenzylidene) -D-sorbitol was prepared by the following procedure as a powdery diacetal clearing agent.
(A) Into a 1 L four-necked cylindrical reaction flask equipped with a thermometer, nitrogen inlet, and mechanical stirrer, D-sorbitol (56.78 g, 0.312 mol), camphorsulfonic acid (1.8 g), 4-n-Butylbenzaldehyde (91.8 g, 0.567 mol) and methanol (613 g) were charged and allowed to react for 48 hours at room temperature to form a first reaction mixture.
(B) The first reaction mixture was filtered to remove the mother liquor, and 300 g of methanol was newly added and neutralized until the pH value reached 8 while stirring. Thereafter, potassium borohydride powder (1.1 g, purity> 96%) and ultramarine blue (0.6 g) are added to the first reaction mixture and stirred for 1 hour to obtain a second reaction solution.
(C) Filter the second reaction solution and collect a solid precipitate from the second reaction solution. Next, the solid precipitate was washed with a 40% by weight methanol solution, dried, and pulverized, whereby 1,3: 2,4-di (4- n-Butylbenzylidene) -D-sorbitol (108.4 g, 81.35% yield (calculated from theoretical mass 133.2 g)) is obtained. Based on the total weight of the powdered diacetal clearing agent, the amount of ultramarine blue is about 0.6% by weight.

The powdery diacetal clearing agent according to Example 8 has the following characteristics.
i, melting point: 237.07 ° C., crystallization temperature: 208.36 ° C.
ii, ¹ H-NMR spectrum (400 MHz, d ₆ -DMSO) δ 7.40-7.30 (dd, 4H), 7.20-7.15 (dd, 2H), 5.61 (s, 2H), 4.81 (d, 1H), 4.41 (t, 1H), 4.20 to 4.09 (m, 3H), 3.88 (s, 1H), 3.85 to 3.80 (m, 1H), 3.79 to 3.70 (m, 1H), 3.62 to 3.58 (m, 1H), 3.42 to 3.38 (m, 1H), 2.58 (t, 4H) 1.60 to 1.45 (m, 4H), 1.35 to 1.25 (m, 4H), 0.90 (t, 6H).
iii, FTIR spectrum data: λ 3239, 2955, 2932, 2858, 1618, 1516, 1458, 1420, 1399, 1370, 1341, 1328, 1310, 1263, 1223, 1167, 1099, 1054, 1018, 980, 945, 883 , 831, 768, 727, 663, 639, 622, 574, 554, 533 cm ⁻¹ .
iv, UV / VIS spectrum data: Absorbance at 262 nm: 0.8117; Absorbance at 649 nm: 0.0044.
v, Ash content: 0.53%.
vi, Purity by LC: 98.15%.
vii, GC analysis result of aromatic aldehyde residue: 4-n-butylbenzaldehyde is not detected.

<Test Example 1>
Test Example 1 relates to particle size and yellowness index. In this test example, powdered diacetal clearing agents according to Examples 1 to 8 and Comparative Examples 2 and 3, commercially available products Millad ^{(registered trademark)} 3988i, Geniset ^{(registered trademark)} DXR, and Millad ^{(registered trademark)} 3940 Samples for measuring particle size and color appearance were used.

Each of the samples was pulverized with an RT-25 airflow type ultrafine powder high-speed pulverizer, and then the particle size distribution was measured with a laser diffraction particle size analyzer. d ₉₇ and the result of the median particle size listed in Table 2.

  Furthermore, in order to measure the degree of yellowing, the samples were each heat aged at 200 ° C. in a circulating oven for 2 hours. The yellowness index of each sample at room temperature (about 25 ° C. to 30 ° C.) and the yellowness index of each sample after heat aging were measured for comparison. The measurement results are shown in Table 2.

Table 2: transparent powders diacetal Examples 1 8, Comparative Examples 2 and 3, the commercial product Millad ^(TM) 3988i, Geniset ^(R) DXR, and Millad ^(R) 3940 _{d 97,} Median particle size, yellowness index at room temperature (YI ₀ ), and yellowness index after 2 hours of heat aging (YI ₁ ).

According to Table 2, none of the powdery diacetal clarifying agents of Examples 1-8, it was found that d ₉₇ is less than the commercial products described above and Comparative Example 2. Similarly, all of the clearing agent powdery diacetals of Examples 1 to 8 have an average particle size smaller than that of Comparative Example 2 and the commercially available product.
In the case of a powdery diacetal clearing agent composed of 1,3: 2,4-di (4-methylbenzylidene) -D-sorbitol, the sample according to Example 7 is d ₉₇ and median rather than the sample according to Comparative Example 3. Both particle sizes were small. The above results show that inorganic silicon-containing compounds having a pH of 6 to 12 are useful for improving the dispersibility of the powdered diacetal clearing agent. The powdery diacetal clearing agents according to Examples 1 to 8 were superior in dispersibility to the powdery diacetal clearing agents according to Comparative Examples 2 and 3 and commercially available products.

The degree of yellowing, YI ₀ powdery diacetal clarifying agents according to Examples 1-8 is lower than the YI _0, such commercially available products as described above and Comparative Example 2. YI ₁ still shows a similar situation.
In light of the comparison results of Example 7 and Comparative Example 3, the powdered diacetal clearing agent according to Comparative Example 3 became a brown gel after heat aging, but the diacetal clearing agent of Example 7 remained white. It was. The above results show that the powdered diacetal clearing agents according to Examples 1-8 have better color stability than Comparative Examples 2, 3 and commercial products, and therefore the powdered diacetal clearing agent according to the present invention By using it, the occurrence of yellowing can be effectively suppressed during plastic processing.

<Test Example 2>
Test Example 2 relates to dispersibility. In this test example, an electron microscope (field emission scanning electron microscope) was used to compare the dispersibility of Example 4, Comparative Example 2, and a commercially available powdered diacetal clearing agent such as Geniset ^{(registered trademark)} DXR. (FE-SEM), JEOL JSM-6700F). Example 4, Comparative Example 2, and commercially available product Geniset ^{(registered trademark)} DXR electron microscope images at a magnification of 2000X are shown in FIG. 1 to FIG. 3, respectively, and the electron microscope images at a magnification of 5000 × are shown in FIG. 4 to 6.

Compared with FIGS. 2, 3, 5, and 6, as shown in FIGS. 1 and 4, the powdered diacetal clearing agent according to Example 4 has the best dispersibility. As shown in FIG.2 and FIG.5, a part of powder of the powdery diacetal transparent agent which concerns on the comparative example 2 has aggregated remarkably. As shown in FIGS. 3 and 6, agglomeration status of commercial products Geniset ^(TM) DXR was more serious than powdery diacetal clarifying agents described above.

  This indicates that the inorganic silicon-containing compound has an important influence on improving the dispersibility of the powdered diacetal clearing agent and preventing aggregation.

<Test Example 3>
Test Example 3 relates to fluidity and operability. In this test example, the powdered diacetal clearing agent prepared in Example 4 is pulverized again with an RT-25 air flow type ultrafine powder and a high-speed pulverizer to obtain a pulverized sample of Example 4.

In this test example, the ground sample of Example 4 and the commercial product Millad ^{(registered trademark)} 3988i are analyzed using a BT-1000 powder flowability tester according to the manual, and its fluidity is measured.

Liquidity is indicated by the following data:
i. The smaller the angle of repose, the better the powder flowability.
ii, the smaller the spatula angle, the better the powder flowability.
iii, the collapse angle is an angle at which the powder disposed at the repose angle collapses due to a predetermined external force.
The iv and angle difference is the difference between the angle of repose and the collapse angle, and the larger the difference, the better the powder flowability.

“Dispersibility” means the degree of dispersion of the powder in the air, and the greater the value of the degree of dispersion, the higher the degree of dispersion of the powder. A 10 g sample was weighed and added to the inlet of the device via a metal funnel. Thereafter, from the immediately opened outlet, the sample falls freely to the receiving tray. Thereafter, the storage tray is taken out, and the weight (m) of the powder in the storage tray is weighed and recorded. The above-described steps are repeated twice to obtain the average value of m, and then the dispersibility is calculated by the following formula.
Dispersity = [(10−m) / 10] * 100%

  Table 3 shows the measurement results of fluidity, repose angle, spatula angle, collapse angle, angle difference, and powder dispersibility. The operability of the sample is also shown in Table 3.

Table 3: shows fluidity of Example 4 and commercially available products Millad according to ^{(registered trademark)} 3988I powdery diacetal transparent, dispersible, the operability.

<Test Example 4>
Test Example 4 relates to the powder flow function. The powder flow function of the powdered diacetal clearing agent according to Example 4 and Comparative Example 2 is a 236 cc standard plate, a Think Brookfield PFT ^{(registered trademark)} powder flow tester (manufactured by Think Brookfield Engineering Laboratories, Inc .; Operation Software: Powder Pro Flow V1 .3 Build 23). The powder flow tester measured the powder flow according to the manual of the powder flow tester in a state where the consolidation stress and uniaxial fracture strength (kPa) were provided.

In this test example, 100 g of powdered diacetal clearing agent according to Example 4 and Comparative Example 2 was pulverized with an RT-25 air flow type ultrafine powder high-speed pulverizer, and then placed on a standard plate. Use to press.
The analysis results for the consolidation stress and uniaxial fracture strength are shown in FIG. As shown in FIG. 7, the slope of the powdery diacetal clearing agent of Example 4 was clearly smaller than the slope of the powdery diacetal clearing agent of Comparative Example 2.

  In light of the tests described above, it can be seen that inorganic silicon-containing compounds are significantly useful for improving the flowability of powdered diacetal clearing agents.

<Test Example 5>
Test Example 5 relates to the characteristics of the plastic product. In this test example, the powdered diacetal clearing agent according to Example 4 and Comparative Example 2 was used, and eight different polyolefin products, which were plaques each having a thickness of 1.5 mm, were produced as samples used for measurement. .

All of the plaques of Samples 1 to 8 were produced by the following steps.
(A) The plastic raw material and the polymer are mixed in the ratio shown in Table 4 and stirred, and at 180 ° C., 190 ° C., 215 ° C., 215 ° C., 215 ° C. and 190 ° C., using an extruder. Are set, and granulation is performed under a rotation condition of 40 rotations (rpm) per minute. The units of amounts listed in Table 4 are resin parts by weight (PHR) per 100 parts by weight.
(B) The mixture has five heating temperatures of 180 ° C., 195 ° C., 210 ° C., 220 ° C., 220 ° C. and a single screw with a length / diameter ratio (L / D) of 22/1. An injection molding machine (YC V-90, manufactured by Year-Chance Machinery) is filled.
(C) The granular resin composition is injected into a mold having a size of 70 mm × 50 mm × 1.5 mm at 30 ° C. to obtain a plaque to be provided for measurement.

  Table 4: Amount of powdery diacetal clearing agent and polyolefin according to Example 4 and Comparative Example 2 (unit: PHR).

The properties of polyolefin products were measured by the following equipment and methods.
1. Yellowness Index plaques after thermal aging was measured on HunterLab ColorFlex ^(TM) EZ Color meter.
2. Plaque haze was measured using a BYK Gardner XL-211 haze meter according to ASTM standard test method D1003-61.
3. Plaque crystallization temperature was measured using a differential scanning calorimeter thermal analyzer.
4). The appearance of Samples 1-8 was evaluated by three persons skilled in the art. The results were obtained from a total score scored by three persons skilled in the art. “1” indicates that the plaque is yellow and has low transparency. “2” indicates that the plaque is yellow and has transparency. “3” indicates that the plaque is light yellow and has transparency. “4” indicates that the plaque is colorless and transparent but not completely transparent. “5” indicates that the plaque is colorless and completely transparent. The total score indicates that the higher the plaque, the better the appearance. The measurement results are shown in Table 5.

  Table 5: Total score of appearance, YI, haze, and crystallization temperature of samples 1-8.

According to the results shown in Table 5, the haze values and crystallization temperatures of samples 2, 4, 6, and 8 are close to the haze values and crystallization temperatures of samples 1, 3, 5, and 7, respectively. It turns out that it is a thing. The plaque according to Example 4 (Samples 2, 4, and 6) was compared with the plaque according to a comparative example (Samples 1, 3, and 5). The yellowness index of sample 2 is smaller than the yellowness index of sample 1, the yellowness index of sample 4 is smaller than the yellowness index of sample 3, and the yellowness index of sample 6 is the yellowness index of sample 5. Less than degree index. The plaque according to Example 4 (Samples 2, 4, 6) and the plaque according to Comparative Example (Samples 1, 3, 5) were compared, and the total scores of Samples 2, 4, 6, and 8 were respectively It is higher than the total score of 1, 3, 5, and 7.
According to the results described above, it was demonstrated that the powdered diacetal clearing agent can be made excellent in color and thermal stability with respect to plastic products.

<Test Example 6>
Test Example 6 relates to the characteristics of the plastic product. In this test example, powdered diacetal clearing agents according to Examples 1, 4, 6 to 8, Comparative Examples 1 to 3, and commercial products Geniset ^{(registered trademark)} DXR and LM30 are polypropylene random polymer (ST611) and others, respectively. The polyolefin product samples 10-19, which are 1.5 mm thick plaques, were prepared.

As shown in Table 6, Examples 1, 4, 6-8, Comparative Examples 1-3, and commercially available products Geniseet ^{(registered trademark)} DXR and LM30 powdered diacetal clearing agent, respectively, polypropylene random polymer ( The samples 10 to 19 were prepared by mixing ST611), a primary antioxidant, a secondary antioxidant, and an acid scavenger. Also, a polypropylene composition produced as a control sample without adding any powdered diacetal clearing agent or diacetal commercial product is designated as sample 9.

  Table 6: Reagents and their amounts for the preparation of polypropylene compositions.

  All of the polypropylene compositions were filled into an injection molding machine (YC V-90, manufactured by Year-Chance Machinery). A 22/1 length / diameter ratio (L / D) screw was used and the temperatures were set at 180 ° C, 195 ° C, 210 ° C, 225 ° C, 230 ° C. The granulated polypropylene composition was then injected into a mold with dimensions of 50 millimeters * 50 millimeters * 1 millimeter at 30 ° C. to obtain Samples 9-19.

The release odor when extruding the polypropylene composition from the die was evaluated by three persons skilled in the art. “0” indicates that the polypropylene composition emits an odor that does not differ from the odor of the control sample. “1” indicates that the polypropylene composition emits an odor that is slightly different from the odor of the control sample. “2” indicates that the polypropylene composition emits an odor that is slightly different from that of the control sample. “3” indicates that the polypropylene composition emits an odor that can be perceived as different from the odor of the control sample. “4” indicates that the polypropylene composition emits an odor significantly different from that of the control sample. “5” indicates that the polypropylene composition emits malodor.
Table 7 shows the total evaluation score by three persons skilled in the art. A lower total score indicates that the sample plaque is not emitting malodor.

  For evaluation of white spots, 10 plaques extruded from the die were collected for each sample, and the visible white spots on the collected 10 plaques were calculated and totaled by three people. “0” indicates that no white spots can be found in the plaque of the sample. “1” indicates that the plaque had a total of 1 to 3 white spots. “2” indicates that the plaque had a total of 4-10 white spots. “3” indicates that the plaque had a total of 11-20 white spots. “4” indicates that the plaque had a total of 21-50 white spots. “5” indicates that the plaque had a total of more than 50 white spots. The smaller the white point, the lower the degree of aggregation of the powdered diacetal clearing agent, indicating a more uniform distribution. The measurement results are shown in Table 7.

  Table 7: Supply source of powdery diacetal clearing agent abbreviated as diacetal source, haze value, crystallization temperature (Tc, unit: ° C), odor evaluation, white point evaluation, and yellowness index according to samples 9 to 19.

As shown in Table 7, the total score of odor evaluation of Samples 11-14 was lower than Samples 15-19. The total odor evaluation score of sample 10 was lower than that of sample 15. None of Samples 10-14 showed any white spots on all plaques, but the plaques of Samples 16, 17, and 19 had at least one white spot. Further, the yellowness index of Sample 10 was closer to 0 than that of Samples 9 and 15. The yellowness index of samples 11-14 was closer to 0 than samples 15-19.
This demonstrates that the powdery diacetal clearing agent containing the inorganic silicon-containing compound is useful for preventing the generation of white spots, yellowing, and the emission of malodors in the manufacturing process of plastic products, This will improve the appearance and properties of plastic products.

The powdery diacetal clearing agent according to the present invention has a high purity substantially free of impurities and volatile substances. Such a powdery diacetal clearing agent has the property of avoiding floating in the air while having excellent fluidity. Further, the powdered diacetal clearing agent does not emit an unpleasant odor during processing of the plastic, and can prevent yellowing of the final plastic product even when processed at a high temperature such as 190 ° C.
Therefore, the powdery diacetal clearing agent according to the present invention is more widely applied and not only excellent in fluidity, but also can make the final plastic product excellent in safety, color, and thermal stability. .

  While many features and advantages of the invention have been set forth in the foregoing description, together with details of the structure and features of the invention, the above disclosure is illustrative only. The shape and size may be varied in detail with respect to the arrangement of components in the technical features of the invention to the full extent indicated by the broad general meaning of the terms expressed in the appended claims.

A Comparative Example 2
B Example 4
C A line representing a measure of whether or not it has very high adhesion D A line representing a measure of whether or not it has adhesiveness E A line representing a measure of whether or not it has fluidity

Claims (20)

A powdered diacetal clearing agent,
A diacetal compound selected from the group consisting of compounds represented by the following general formulas (I) to (V);
Here, R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, 1 to 4 carbon atoms, fluoro, A substituent selected from the group consisting of an alkoxycarbonyl group having chloro and bromo, a and b are each independently an integer selected from 0 to 3;
And inorganic silicon-containing compound, was perforated with 6 or more and 12 or less of the pH value,
The inorganic silicon-containing compound has a median particle size of 15 micrometers or less;
The amount of the diacetal compound is 96.5 wt% or more, and the amount of the inorganic silicon-containing compound is 0.02 wt% to 3.5 wt% based on the total amount of the powdered diacetal clearing agent. It is characterized by
Powdered diacetal clearing agent.   The powdery diacetal clearing agent according to claim 1, wherein the amount of the inorganic silicon-containing compound is 0.02 wt% to 3.0 wt% based on the total amount of the powdered diacetal clearing agent. .   The powdery diacetal clearing agent according to claim 2, wherein the amount of the inorganic silicon-containing compound is 0.2 wt% to 1.0 wt% based on the total amount of the powdered diacetal clearing agent. .   The diacetal compound includes 1,3: 2,4-di (5-methyl-2-tenylidene) -D-sorbitol, 1,3: 2,4-di (4-methylbenzylidene) -D-sorbitol, Selected from the group consisting of 3: 2,4-di (4-n-butylbenzylidene) -D-sorbitol and 1,3: 2,4-di (3,4-dimethylbenzylidene) -D-sorbitol The powdery diacetal clearing agent according to claim 1, wherein The inorganic silicon-containing compound is sodium potassium aluminosilicate, calcium silicate, calcium calcium aluminosilicate, sodium aluminosilicate, potassium magnesium aluminosilicate, hydrated aluminosilicate, lithium magnesium oxide sodium silicate, and any of them The powdery diacetal clearing agent according to claim 1 , wherein the powdery diacetal clearing agent is selected from the group consisting of combinations.
The powder form according to claim 1 , wherein the inorganic silicon-containing compound has a pH value of 8 or more and 10 or less, and a median particle size of the inorganic silicon-containing compound is 10 micrometers or less. Diacetal clearing agent. The powdery diacetal clearing agent according to claim 6 , wherein the inorganic silicon-containing compound is sodium aluminosilicate containing a trisulfur radical anion. The inorganic silicon-containing compound is a exfoliated montmorillonite silica nanomaterial having a median particle size of less than 1 micrometer, and the exfoliated montmorillonite silica nanomaterial has a pH value of 9 to 10. The powdery diacetal clearing agent according to claim 1 . It said inorganic silicon-containing compound is a lithium magnesium oxide sodium silicate having a median particle size of less than 50 nanometers, pH value of the lithium magnesium sodium oxide silicate, to claim 1, characterized in that 9-10 The powdery diacetal clearing agent as described. A method for producing a powdered diacetal clearing agent,
(A) A first reaction mixture is obtained by mixing an aromatic aldehyde, a polyol, and an acid catalyst in an organic polar solvent, and the equivalent ratio of the aromatic aldehyde to the polyol is 2: 1 to 2: A step that is 2,
(B) A second reaction mixture is obtained by adding a hydrogenating agent and an inorganic silicon-containing agent to the first reaction mixture, and the equivalent ratio of the hydrogenating agent to the aromatic aldehyde is 0.01. Greater than 1: the inorganic silicon-containing agent has a pH value of 6-12, and the amount of the inorganic silicon-containing agent used is 0.02% by weight to 3.% based on the amount of the aromatic aldehyde. 5 wt% der is, the inorganic silicon-containing compounds, that have a median particle size of 15 micrometers or less steps,
(C) While filtering the second reaction mixture and drying the filtered second reaction mixture, a powdery diacetal clearing agent is obtained , and the powdery diacetal clearing agent has the following general formula ( I) 96.5 wt% or more of a diacetal compound selected from the group consisting of compounds represented by (V),

Here, R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, 1 to 4 carbon atoms, fluoro, chloro, and is a substituent selected from the group consisting of alkoxycarbonyl groups having bromo, a and b are each independently characterized by having a step, Ru integer der selected from 3 0 to ,
A method for producing a powdery diacetal clearing agent. The method for producing a powdery diacetal clearing agent according to claim 10 , wherein an equivalent ratio of the polyol and the aromatic aldehyde is from 2: 1.05 to 2: 1.3. The method for producing a powdery diacetal clearing agent according to claim 10 , wherein an equivalence ratio of the hydrogenating agent and the aromatic aldehyde is 0.03: 1 to 0.3: 1. The powdery diacetal transparent agent according to claim 10 , wherein the amount of the inorganic silicon-containing agent is 0.2 wt% to 1.0 wt% based on the amount of the aromatic aldehyde. Method. The method for producing a powdery diacetal clearing agent according to claim 10 , wherein the aromatic aldehyde is a thiophenecarboxaldehyde compound, a benzaldehyde compound, or a combination thereof. The thiophene carboxaldehyde-based compound is unsubstituted thiophene carboxaldehyde or thiophene carboxaldehyde having 1 to 3 substituents, and the substituent is an alkyl group having 1 to 4 carbon atoms, 1 to 4 The powder according to claim 14 , which is a substituent selected from the group consisting of an alkoxy group having 5 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms, fluoro, chloro, and bromo. Of manufacturing a diacetal transparent agent. The method for producing a powdery diacetal transparent agent according to claim 10 , wherein the aromatic aldehyde is 5-methyl-2-thiophenecarboxaldehyde. The benzaldehyde-based compound is an unsubstituted benzaldehyde or a benzaldehyde having 1 to 3 substituents, and the substituent includes an alkyl group having 1 to 4 carbon atoms and an alkoxy having 1 to 4 carbon atoms. The production of a powdered diacetal clearing agent according to claim 14 , characterized in that it is a substituent selected from the group consisting of a group, an alkoxycarbonyl group having 1 to 4 carbon atoms, fluoro, chloro, and bromo. Method. The powdery diacetal clearing agent according to claim 10 , wherein the aromatic aldehyde is selected from the group consisting of 4-methylbenzaldehyde, 4-n-butylbenzaldehyde, and 3,4-dimethylbenzaldehyde. Manufacturing method. The hydrogenating agent is sodium hydride, potassium hydride, aluminum hydride, sodium cyanoborohydride, diisobutylaluminum hydride, lithium borohydride, sodium borohydride, potassium borohydride, calcium, borohydride or The method for producing a powdery diacetal clearing agent according to claim 10 , which is an arbitrary combination thereof. The method for producing a powdery diacetal clearing agent according to claim 19 , wherein the hydrogenating agent is sodium borohydride or potassium borohydride.